Structure for electrochemical device to improve safety and electrochemical device comprising the same

ABSTRACT

Disclosed is a sealed structure for an electrochemical device having a hollow space therein, further comprising a material generating gases via thermal decomposition in the hollow space. Also, disclosed is an electrochemical device comprising a cathode, an anode, a separator, an electrolyte, a casing for the device, and the structure for the electrochemical device.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a divisional of U.S. patent application Ser.No. 12/310,603 filed Feb. 25, 2009, which is a national phase entryunder 35 U.S.C. §371 of International Application No. PCT/KR2007/004058,filed Aug. 24, 2007, published in English, which claims the benefit ofKorean Patent Application No. 10-2006-0081347, filed Aug. 25, 2006. Thedisclosures of said applications are incorporated by reference herein.

TECHNICAL FIELD

The present invention relates to a structure for an electrochemicaldevice containing a material capable of imparting excellent safety tothe device even when the internal pressure or voltage of the deviceabnormally increases, and an electrochemical device comprising the same.

BACKGROUND ART

Recently, as electronic appliances have been downsized and lightened,and the use of portable electronic appliances has been generalized, manyactive studies have been conducted to develop lithium secondarybatteries having high energy density.

A lithium secondary battery comprises a cathode and an anode, eachformed of a material capable of lithium ionintercalation/deintercalation. An organic electrolyte or polymerelectrolyte is injected between the cathode and the anode. Such lithiumsecondary batteries generate electric energy via redox reactionsoccurring upon lithium ion intercalation/deintercalation at the cathodeand the anode.

However, such lithium secondary batteries have problems related withtheir safety, such as ignition and explosion, caused by the use of anon-aqueous electrolyte. The above problems become more serious as thecapacity density of a battery increases. Particularly, when a battery isovercharged to a voltage higher than the normal drive voltage, anexcessive amount of lithium is deintercalated from the cathode and thelithium produces dendrite at the anode so that both the cathode and theanode become thermally unstable, resulting in a rapid exothermicreaction including decomposition of the electrolyte. Due to theexothermic reaction, the battery causes a thermal runaway phenomenonfollowed by ignition and explosion, and shows a serious problem relatedwith its safety.

Many attempts have been made to inhibit such ignition or explosion of abattery caused by overcharge or an increase in the temperature insidethe battery. For example, an additive for a non-aqueous electrolyte hasbeen used. However, it is necessary to introduce a great amount of theadditive in order to improve the safety of a battery by using theadditive for a non-aqueous electrolyte. Such direct introduction of theadditive may cause degradation of the quality of the battery.

Therefore, there is a need for developing a novel means to improve thesafety of an electrochemical device including a battery.

DISCLOSURE OF THE INVENTION Technical Problem

Therefore, the present invention has been made in view of theabove-mentioned problems. It is an object of the present invention toprovide a structure for an electrochemical device which has a hollowspace therein, comprises a material capable of improving the safety ofthe device in the hollow space, and allows easy control of the amount ofthe material contained in the hollow space.

It is another object of the present invention to provide a structure foran electrochemical device which causes the material contained in thehollow space thereof, preferably a material generating gases via thermaldecomposition, to be discharged to the exterior of the structure so thatthe material generates gases via thermal decomposition before or afterit is discharged to the exterior of the structure, and thus can improvethe safety of the device by the gases generated in the exterior of thestructure or the gases discharged to the exterior of the structure.

It is still another object of the present invention to provide anelectrochemical device comprising the structure for an electrochemicaldevice.

Technical Solution

In order to achieve the above-mentioned object, the present inventionprovides a structure for an electrochemical device comprising: a hollowcylindrical tube; a first member formed of a polymer and sealing one endof the hollow cylindrical tube; and a second member formed of a polymeror a metal, and sealing the other end of the hollow cylindrical tube,the structure further comprising a material generating gases via thermaldecomposition in a hollow space thereof.

Also, the present invention provides a structure for an electrochemicaldevice comprising: a tube having two or more hollow cylindrical tubesconnected to each other longitudinally by way of a polymer; a thirdmember for sealing one end of the tube; and a fourth member for sealingthe other end of the tube, the structure further comprising a materialgenerating gases via thermal decomposition in a hollow space thereof.

Further, the present invention provides a structure for anelectrochemical device comprising: a hollow cylindrical tube having atleast one opening on a surface thereof and sealed at both ends thereof;and a polymer member for sealing the opening, the structure furthercomprising a material generating gases via thermal decomposition in ahollow space thereof.

Further, the present invention provides an electrochemical devicecomprising a cathode, an anode, a separator, an electrolyte, a casing,and any one structure selected from the above three types of structures.

The structure for an electrochemical device is a sealed structure havinga hollow space therein, comprises a material generating gases viathermal decomposition to improve the safety of the electrochemicaldevice using the same structure inside the hollow space, and allows easycontrol of the amount of the material contained in the hollow space.

Additionally, the structure according to the present invention does notaffect an electrochemical device when the device is in a normaltemperature/voltage condition. However, when the internal temperature ofthe device abnormally increases or the device is subjected to anover-voltage state due to overcharge, a predetermined portion of thestructure, preferably a portion formed of a polymeric component maymelt. Such melting of a portion of the structure causes the inner partof the structure to be exposed to the exterior. At this time, thematerial contained in the hollow space of the structure, i.e. thematerial capable of generating gases via thermal decomposition, may bedischarged to the exterior of the structure before it is thermallydecomposed to generate gases. Otherwise, the material may generate gasesvia thermal decomposition before it is discharged to the exterior of thestructure. The gases (carbon dioxide and/or nitrogen) generated at theexterior of the structure or discharged to the exterior of the structurecan contribute to improvement of the safety of the device. The gasesgenerated via thermal decomposition include a great amount of inertgases, which can interrupt any materials capable of heat emission insidethe device from being in contact with oxygen, and can improve the safetyof the device.

Further, the electrochemical device comprising the structure accordingto the present invention may be provided with a pressure-sensitivedevice, such as a CID (current interruption device), which interruptscharging of the device or converts a charging condition into adischarging condition by detecting variations in pressure, or may beprovided with a pressure regulating valve, such as a vent, which allowsemission of heat or gases inside the device to the exterior by detectingvariations in the pressure. In this case, the gases discharged to theexterior of the structure or generated via the thermal decomposition ofthe material discharged to the exterior of the structure allow thepressure-sensitive device or the pressure regulating valve to operate,thereby improving the safety of the device.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing and other objects, features and advantages of the presentinvention will become more apparent from the following detaileddescription when taken in conjunction with the accompanying drawings inwhich:

FIGS. 1 to 7 each are plan views illustrating preferred embodiments ofthe structure for an electrochemical device according to the presentinvention;

FIG. 8 is a graph showing the temperature and the voltage as a functionof time, and the time required for a CID (current interruption device)to cause a short, in the battery according to Example 3; and

FIG. 9 is a graph showing the temperature and the voltage as a functionof time, and the time required for a CID (current interruption device)to cause a short, in the battery according to Comparative Example 1.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be explained in more detail.

The material contained in the hollow space of the structure according tothe present invention includes a material generating gases via thermaldecomposition, i.e. a material decomposed in itself by heat to generategases, such as carbon dioxide or nitrogen. Non-limiting examples of thematerial include organic peroxides, carbonate compounds, azo compounds,hydrazide compounds, carbazide compounds, or the like. Such compoundsmay be used alone or in combination in the structure for anelectrochemical device according to the present invention.

If the material generating gases via thermal decomposition is notincorporated into the structure according to the present invention, butis incorporated directly into an electrochemical device, it causes areaction in voltage ranges of 0˜3V and 3.5V˜4.5V, resulting indegradation of the quality of the electrochemical device. Therefore, itis necessary to incorporate the gas-generating compound into the hollowspace inside the structure for an electrochemical device so as to solvethe above-mentioned problem.

Non-limiting examples of the organic peroxide include dibenzoylperoxide, di-(2,4-dichlorobenzoyl peroxide),bis(3-methyl-3-methoxybutyl)peroxy dicarbonate), t-butylperoxyneodecanoate, t-butyl peroxypivalate, dilauroyl peroxide,distearyl peroxide, t-butyl peroxy 2-ethylhexanoate, t-butylperoxylaurate, t-butyl peroxy 2-ethylhexyl carbonate, t-butylperoxybenzoate, t-hexyl peroxybenzoate, dicumyl peroxide, t-butyl cumylperoxide, di-t-butyl peroxide,2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, or the like. The aboveorganic peroxides may be used alone or in combination.

Non-limiting examples of the carbonate compound include sodiumbicarbonate (NaHCO₃).

Non-limiting examples of the azo compound include2,2′-azobis(isobutyronitrile), 2,2′-azobis(2-methylbutyronitrile),2,2′-azobis(2-methylvaleronitrile),2,2′-azobis(2,3-dimethylbutyronitrile),2,2′-azobis(2-methylcapronitrile),2,2′-azobis(2,4-dimethylvaleronitrile),1,1′-azobis(1-cyclohexylcyanide), 2,2′-dimethoxy-2,2′-azopropane,2,2′-diethoxy-2,2′-azopropane, 2,2′-dipropoxy-2,2′-azopropane,2,2′-diisopropoxy-2,2′-azopropane, 2,2′-dibutoxy-2,2′-azopropane,2,2′-diisobutoxy-2,2′-azopropane, 2,2′-dineobutoxy-2,2′-azopropane,azodicarbonamide, or the like. Additionally, the above azo compounds maybe used alone or in combination.

Non-limiting examples of the hydrazide compound includebenzosulfonylhydrazide, 4,4′-oxybis(benzenesulfonylhydrazide),p-toluenesulfonylhydrazide, polybenzenesulfonylhydrazide,bis(hydrazosulfonyl)benzene, 4,4′-bis(hydrazosulfonyl)biphenyl,diphenyldisulfonylhydrazide, diphenylsulfone-3,3-disulfonylhydrazide, orthe like. Additionally, the above hydrazide compounds may be used aloneor in combination.

Further, non-limiting examples of the carbazide compound includeterephthalzide, and other fatty acid azides and aromatic acid azides.The above carbazide compounds may be used alone or in combination.

The structure for an electrochemical device according to the presentinvention includes the following three preferred embodiments.

In the first embodiment, the structure for an electrochemical devicecomprises: a hollow cylindrical tube; a first member formed of a polymerand sealing one end of the hollow cylindrical tube; and a second memberformed of a polymer or a metal and sealing the other end of the hollowcylindrical tube, the structure further comprising a material generatinggases via thermal decomposition in a hollow space thereof.

The first embodiment of the structure for an electrochemical device ischaracterized in that either or both of the first member and the secondmember melt at a temperature higher than the normal drive temperature ofthe device or under a voltage higher than 4.3V. Herein, the temperaturehigher than the normal drive temperature preferably ranges from 70° C.to 200° C.

When either or both of the first member and the second member melt inthe first embodiment of the structure for an electrochemical device, theinner part of the structure can be exposed to the exterior.

There is no particular limitation in the polymer forming the firstmember and the second member, as long as the polymer melts at atemperature higher than the normal drive temperature of the device orunder a voltage higher than 4.3V. Non-limiting examples of such polymersinclude silicone resins, acrylic resins, urethane resins, epoxy resins,rubber, polyethylene, polypropylene, polybutene, polyacetaldehyde,polyformaldehyde, polypropylene oxide, polymethyl methacrylate,polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, orthe like. The above polymers may be used alone or in combination. Thepolymer forming the first member and the polymer forming the secondmember may be the same or different.

Additionally, the hollow cylindrical tube may be formed of a polymer ormetal. Particularly, the hollow cylindrical tube forms the skeleton ofthe structure for an electrochemical device according to the presentinvention. The hollow cylindrical tube preferably has durability,electrochemical stability and thermal stability.

The polymer forming the hollow cylindrical tube may be the same as ordifferent from the polymer forming the first member and the secondmember. Preferably, the polymer forming the hollow cylindrical tube hasa higher melting point than the melting point of the polymer forming thefirst member and the second member. More preferably, the polymer formingthe hollow cylindrical tube does not melt at a temperature higher thanthe normal drive temperature of the device or under a voltage higherthan 4.3V but maintains its original shape. Non-limiting examples ofsuch polymers include ethylene vinyl acetate (EVA), polystyrene,polyphenylene ether (PPE), polychlorotrifluoroethylene, polyvinylchloride (PVC), polyethylene terephthalate (PET), polyamide,polycaprolactam, polycarbonate (PC), poly-(p-xylene), polyimide (PI),polyoxybenzoate (POB), polyetheretherketone (PEEK), polyphenylenesulfide (PPS), polyether sulfone (PES), polysulfone (PSU), siliconeresins, acrylic resins, urethane resins, epoxy resins, rubber,polyethylene, polypropylene, polybutene, polyacetaldehyde,polyformaldehyde, polypropylene oxide, polymethyl methacrylate,polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, orthe like. The above polymers may be used alone or in combination.

Additionally, there is no particular limitation in the metal forming thehollow cylindrical tube and the second member, as long as the metal hasa higher melting point than the melting point forming both the firstmember and the second member. Preferably, the metal does not melt at atemperature higher than the normal drive temperature of the device orunder a voltage higher than 4.3V. Non-limiting examples of such metalsinclude nickel, copper, aluminum, titanium, chrome, carbon, iron,cobalt, molybdenum, gold, silver, vanadium, SUS (stainless steel),alloys thereof, or the like. The above metals may be used alone or incombination.

FIG. 1 is a plan view showing a preferred embodiment of the structurefor an electrochemical device according to the present invention. Thestructure is the first embodiment of the structure that comprises ahollow cylindrical tube 10 and a first member 20 and a second member 30sealing both ends of the hollow cylindrical tube, and further comprisesa material generating gases via thermal decomposition in the hollowspace thereof. The polymer member and the end of the hollow cylindricaltube may be linked with each other, for example, by using a hot fusionprocess so that the end is sealed. Herein, the polymer member isintroduced into the end of the hollow cylindrical tube after it issealed. If the first member 20 and/or the second member 30 is formed ofthe same material as the hollow cylindrical tube 10, either end or bothends of the hollow cylindrical tube may be subjected to hot fusion toseal the structure without using a separate first member and/or secondmember.

FIGS. 2 and 3 are plan views each showing another structure according tothe first embodiment of the present invention, each structurecomprising: a hollow cylindrical tube 10; a first member 20 formed of apolymer and sealing one end of the hollow cylindrical tube; and a secondmember 30 formed of a metal and sealing the other end of the hollowcylindrical tube, and further comprising a material generating gases viathermal decomposition inside the hollow space thereof. Herein, the firstmember formed of a polymer is introduced into one end of the hollowcylindrical tube in the form of a septum or capsule.

The second embodiment of the structure for an electrochemical deviceaccording to the present invention comprises: a tube having two or morehollow cylindrical tubes connected to each other longitudinally by wayof a polymer; a third member for sealing one end of the tube; and afourth member for sealing the other end of the tube, the structurefurther comprising a material generating gases via thermal decompositionin a hollow space thereof.

The second embodiment of the structure is characterized in that thepolymer for connecting the two or more hollow cylindrical tubes melts ata temperature higher than the normal drive temperature of the device orunder a voltage higher than 4.3V, so that the connected tubes areseparated from each other and the inner part of the sealed structure isexposed to the exterior. Herein, the temperature higher than the normaldrive temperature of the device preferably ranges from 70° C. to 200° C.

In the second embodiment of the structure, the polymer for connectingthe two or more hollow cylindrical tubes may be present in the form of atube or plate. However, there is no particular limitation in the shapeand thickness of the polymer.

Additionally, there is no particular limitation in the polymer forconnecting the two or more hollow cylindrical tubes, as long as thepolymer melts at a temperature higher than the normal drive temperatureof the device using the structure or under a voltage higher than 4.3V.Non-limiting examples of such polymers include silicone resins, acrylicresins, urethane resins, epoxy resins, rubber, polyethylene,polypropylene, polybutene, polyacetaldehyde, polyformaldehyde,polypropylene oxide, polymethyl methacrylate, polyvinylidene chloride,polyvinyl fluoride, polyvinylidene fluoride, or the like. The abovepolymers may be used alone or in combination.

In the second embodiment of the structure, the hollow cylindrical tube,the third member and the fourth member may be formed of a polymer ormetal independently from each other.

There is no particular limitation in the polymers forming the hollowcylindrical tube, the third member and the fourth member. Therefore,each of the polymers forming the hollow cylindrical tube, the thirdmember and the fourth member may be the same as or different from thepolymer for connecting the two or more hollow cylindrical tubes.Preferably, each polymer has a higher melting point than the meltingpoint of the polymer for connecting the two or more hollow cylindricaltubes. More preferably, each polymer does not melt at a temperaturehigher than the normal drive temperature of the device or under avoltage higher than 4.3V but maintains its original shape. Non-limitingexamples of such polymers are the same as the polymer forming the hollowcylindrical tube in the first embodiment of the structure.

Additionally, there is no particular limitation in the metal forming thehollow cylindrical tube, the third member and the fourth member, as longas the metal has a higher melting point than the melting point of thepolymer for connecting the two or more hollow cylindrical tubes. Morepreferably, the metal does not melt at a temperature higher than thenormal drive temperature of the device or under a voltage higher than4.3V. Non-limiting examples of such metals are the same as the metalforming the hollow cylindrical tube in the first embodiment of thestructure.

FIG. 4 is a plan view showing a preferred embodiment of the structurefor an electrochemical device according to the present invention. Thestructure comprises a tube having two hollow cylindrical tubes 10, 11connected longitudinally to each other by way of a polymer 40, and athird member 20 and a fourth member 30 formed of a polymer and sealingboth ends of the hollow cylindrical tube, the structure furthercomprising a material generating gases via thermal decomposition in thehollow space thereof.

The third embodiment of the structure for an electrochemical deviceaccording to the present invention comprises: a hollow cylindrical tubehaving at least one opening on a surface thereof and sealed at both endsthereof; and a polymer member for sealing the opening, the structurefurther comprising a material generating gases via thermal decompositionin a hollow space thereof.

The third embodiment of the structure is characterized in that thepolymer member for sealing the opening melts at a temperature higherthan the normal drive temperature of the device or under a voltagehigher than 4.3V, so that the inner part of the sealed structure isexposed to the exterior. Herein, the temperature higher than the normaldrive temperature of the device preferably ranges from 70° C. to 200° C.

There is no particular limitation in the shape and size of the openingformed on the surface of the hollow cylindrical tube.

Also, there is no particular limitation in the shape and size of thepolymer member for sealing the opening. For example, the polymer member50 may have a notch-like shape indented into the hollow cylindrical tube10 as shown in FIG. 5, a scratch-like shape formed on the hollowcylindrical tube 10 as a thin layer as shown in FIG. 6, anembossment-like structure protruding out from the hollow cylindricaltube 10 as shown in FIG. 7, or a combined shape thereof.

Additionally, there is no particular limitation in the polymer for thepolymer member, as long as the polymer melts at a temperature higherthan the normal drive temperature of the device using the structure orunder a voltage higher than 4.3V. Non-limiting examples of such polymersinclude silicone resins, acrylic resins, urethane resins, epoxy resins,rubber, polyethylene, polypropylene, polybutene, polyacetaldehyde,polyformaldehyde, polypropylene oxide, polymethyl methacrylate,polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, orthe like. The above polymers may be used alone or in combination.

In the third embodiment of the structure, the hollow cylindrical tubemay be formed of a polymer or metal.

There is no particular limitation in the polymer forming the hollowcylindrical tube. Therefore, the polymer forming the hollow cylindricaltube may be the same as or different from the polymer for the polymermember. Preferably, the polymer has a higher melting point than themelting point of the polymer member. More preferably, the polymer doesnot melt at a temperature higher than the normal drive temperature ofthe device or under a voltage higher than 4.3V but maintains itsoriginal shape. Non-limiting examples of such polymers are the same asthe polymer forming the hollow cylindrical tube in the first embodimentof the structure.

Additionally, there is no particular limitation in the metal forming thehollow cylindrical tube, as long as the metal has a higher melting pointthan the melting point of the polymer for the polymer member. Morepreferably, the metal does not melt at a temperature higher than thenormal drive temperature of the device or under a voltage higher than4.3V. Non-limiting examples of such metals are the same as the metalforming the hollow cylindrical tube in the first embodiment of thestructure.

Meanwhile, the structure for an electrochemical device according to thepresent invention is not limited to the above first through thirdembodiments of the structure. Any combination of the above embodimentsis also included in the scope of the present invention.

Additionally, there is no particular limitation in the size of thestructure for an electrochemical device according to the presentinvention.

The electrochemical device according to the present invention comprisesa cathode, an anode, a separator, an electrolyte, a casing for thedevice and the structure for an electrochemical device according to thepresent invention.

The electrochemical device according to the present invention includesall types of devices in which electrochemical reactions are performed.Particular examples of the electrochemical device include all types ofprimary batteries, secondary batteries, fuel cells, solar cells,capacitors, or the like. Among the secondary batteries, lithiumsecondary batteries, including lithium metal secondary batteries,lithium ion secondary batteries, lithium polymer secondary batteries orlithium ion polymer secondary batteries, are preferred.

In the electrochemical device according to the present invention, thestructure may be incorporated into hollow spaces in the device or theelectrolyte, or as a center pin. The hollow spaces in the device mayinclude a space between a jelly roll-like electrode assembly and thecasing for the device, or a space between a jelly roll-like electrodeassembly and a pouch, but is not limited thereto.

The material contained in the hollow space inside the structure for anelectrochemical device may generate gases via thermal decomposition at ahigh temperature higher than the normal drive temperature of the deviceor a voltage higher than 4.3V, before or after the material isdischarged to the exterior of the structure. The gases include a greatamount of inert gases (carbon dioxide and/or nitrogen), which caninterrupt any materials capable of heat emission inside the device frombeing in contact with oxygen and can improve the safety of the device.

Additionally, the electrochemical device comprising the structureaccording to the present invention may further comprise:

(a) a first safety device that detects variations in the pressure insidethe electrochemical device to interrupt charging of the electrochemicaldevice or to convert a charging condition into a discharging condition;(b) a second safety device that detects variations in the pressureinside the electrochemical device to emit the heat or gas present insidethe electrochemical device; or (c) both the first safety device and thesecond safety device.

Non-limiting examples of the first safety device that may be used in thepresent invention include a pressure-sensitive device, such as aconventional CID known to those skilled in the art. Thepressure-sensitive device may be a monolithic device, or may comprise:(i) a pressure-sensitive member; (ii) an electric wire for conductingcurrent transferred from the pressure-sensitive member; and (iii) amember that responds to the current conducted from the electric wire tointerrupt charging of the electrochemical device or to convert acharging condition into a discharging condition.

The pressure-sensitive device refers to a device that can detect avariation in the pressure inside the sealed electrochemical device, i.e.an increase in the pressure, and can interrupt current flow by itself;or can generate current toward the exterior or a control circuit tointerrupt charging of the electrochemical device. Herein, thepressure-sensitive device may be a monolithic device serving not only asa safety device but also as a pressure-sensitive member. Otherwise, aseparate pressure-sensitive device independent from the safety devicemay be used. However, there is no particular limitation in the type ormechanism of the pressure-sensitive device, as long as the deviceperforms the above-mentioned function in a specific range of pressure.

Particular examples of the pressure-sensitive device includepiezoelectric crystals generating electric current by detecting avariation in the pressure. Additionally, there is no particularlimitation in the pressure range where the pressure-sensitive deviceoperates, as long as the pressure range is out of the conventionalinternal pressure of the electrochemical device and does not allowexplosion.

Additionally, there is no particular limitation in the second safetydevice, as long as the second safety device detects variations in thepressure inside the electrochemical device to emit the heat or gas (e.g.inflammable gas, etc.) present inside the electrochemical device to theexterior. Non-limiting examples of the second safety device include apressure regulating valve, such as a vent.

When the electrochemical device according to the present inventionfurther comprises the first safety device and/or the second safetydevice, the material contained in the hollow space inside the structurefor an electrochemical device may generate gases via thermaldecomposition at a high temperature higher than the normal drivetemperature of the device or a voltage higher than 4.3V, before or afterthe material is discharged to the exterior of the structure.

Under these circumstances, either or both of the first safety device andthe second safety device can operate by detecting a variation in theinternal pressure of the device, including an increase in the pressurecaused by the gases generated in the exterior of the structure ordischarged to the exterior of the structure. Such serial mechanism canimprove the safety of the electrochemical device.

The electrochemical device may be obtained by using a conventionalmethod known to those skilled in the art. In a preferred embodiment ofthe method, the structure according to the present invention is used asa center pin, an electrode assembly is formed by winding a cathode, ananode and a separator interposed between both electrodes around thecenter pin in the form of a jelly roll to provide an electrode assembly,the electrode assembly is introduced in a casing, and then anelectrolyte is injected thereto.

The electrode used in the electrochemical device according to thepresent invention may be manufactured by a conventional method known toone skilled in the art. For example, an electrode active material may bemixed with a solvent, and optionally with a binder, a conductive agentand a dispersant, and the mixture is agitated to provide slurry. Then,the slurry is applied onto a metal collector, and the collector coatedwith the slurry is compressed and dried to provide an electrode.

The electrode active material includes a cathode active material or ananode active material.

Cathode active materials that may be used in the present inventioninclude: lithium transition metal composite oxides, such as LiM_(x)O_(y)(M=Co, Ni, Mn, Co_(a)Ni_(b)Mn_(c)) (e.g. lithium manganese compositeoxides such as LiMn₂O₄, lithium nickel oxides such as LiNiO₂, otheroxides obtained by substituting manganese, nickel and cobalt in theabove oxides partially with other transition metals, orlithium-containing vanadium oxide, etc.); or calcogenides, such asmanganese dioxide, titanium disulfide, molybdenum disulfide, etc.However, the scope of the present invention is not limited thereto.

Anode active materials that may be used in the present invention includethose currently used in anodes for electrochemical devices. Particularexamples of the anode active materials include lithium metal, lithiumalloys, carbon, petroleum coke, activated carbon, graphite or carbonfiber capable of lithium ion intercalation/deintercalation. Other metaloxides capable of lithium intercalation/deintercalation and having apotential vs. Li⁺/Li of less than 2V (for example, TiO₂ or SnO₂) mayalso be used. Particularly, carbonaceous materials, such as graphite,carbon fiber or activated carbon are preferred.

There is no particular limitation in the current collector, as long asthe collector is formed of a highly conductive metal, allows easyattachment of slurry of an electrode active material thereto, and has noreactivity in the drive voltage range of the battery. Non-limitingexamples of a cathode collector include foil formed of aluminum, nickelor a combination thereof. Non-limiting examples of an anode collectorinclude foil formed of copper, gold, nickel, copper alloys or acombination thereof.

The electrolyte may comprise a non-aqueous solvent and an electrolytesalt, and may also include water.

There is no particular limitation in the non-aqueous solvent, as long asthe solvent is one currently used for a non-aqueous electrolyte.Particular examples of the solvent include cyclic carbonates, linearcarbonates, lactones, ethers, sulfoxides, acetonitriles, lactams and/orketones.

Particular examples of the cyclic carbonates include ethylene carbonate(EC), propylene carbonate (PC), butylene carbonate (BC), fluoroethylenecarbonate (FEC), or the like. Particular examples of the linearcarbonates include diethyl carbonate (DEC), dimethyl carbonate (DMC),dipropyl carbonate (DPC), dibutyl carbonate, ethyl methyl carbonate(EMC), methyl propyl carbonate (MPC), or the like. Particular examplesof the lactones include gamma-butyrolactone (GBL) and those of ethersinclude dibutyl ether, tetrahydrofuran, 2-methyltetrahydrofuran,1,4-dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, or the like.Particular examples of the esters include methyl formate, ethyl formate,propyl formate, methyl acetate, ethyl acetate, propyl acetate, methylpropionate, ethyl propionate, butyl propionate, methyl pivalate, or thelike. Additionally, particular examples of the sulfoxides includedimethyl sulfoxide, or the like, and those of the lactams includeN-methyl pyrrolidone (NMP), or the like. Further, particular examples ofthe ketones include polymethylvinyl ketone. Halogen derivatives of theabove organic solvents may also be used. Such organic solvents may beused alone or in combination.

There is no particular limitation in the electrolyte salt, as long asthe electrolyte salt is one currently used for a non-aqueouselectrolyte. Non-limiting examples of the electrolyte salt include saltsrepresented by the formula of A⁺B⁻, wherein A⁺ includes a cationselected from the group consisting of Li⁺, Na⁺ and K⁺, or a combinationthereof, and B⁻ includes an anion selected from the group consisting ofPF₆ ⁻, BF₄ ⁻, Cl⁻, I⁻, ClO₄ ⁻, ASF₆ ⁻, CH₃CO₂ ⁻, CF₃SO₃ ⁻, N(CF₃SO₂)₂ ⁻and C(CF₂SO₂)₃ ⁻, or a combination thereof. Particularly, a lithium saltis preferred. Such electrolyte salts may be used alone or incombination.

Although there is no particular limitation in the separator that may beused in the present invention, a porous separator is preferred, andparticular examples thereof include polypropylene-based,polyethylene-based, and polyolefin-based porous separators.

Further, although there is no particular limitation in the outer shapeof the electrochemical device according to the present invention, theelectrochemical device may have a cylindrical shape using a can, aprismatic shape, a pouch-like shape or a coin-like shape.

Reference will now be made in detail to the preferred embodiments of thepresent invention. It is to be understood that the following examplesare illustrative only and the present invention is not limited thereto.

Example 1 Manufacture of Structure for Electrochemical Device

First, 0.3 g of benzoyl peroxide was introduced into a hollowcylindrical tube having a diameter of 3 mm and a length of 57.5 mm andmade of polypropylene. Then, both ends of the hollow cylindrical tubewere sealed via hot fusion to provide a structure for an electrochemicaldevice.

Example 2 Manufacture of Structure for Electrochemical Device

A structure for an electrochemical device was provided in the samemanner as described in Example 1, except that di(2,4-dichlorobenzoyl)peroxide was used instead of benzoyl peroxide.

Example 3 Manufacture of Electrochemical Device

First, 94 wt % of LiCoO₂ as a cathode active material, 3 wt % ofacetylene black as a conductive agent and 3 wt % of PVDF as a binderwere mixed, and the resultant mixture was added to NMP(N-methyl-2-pyrrolidone) to form cathode slurry, which, in turn, wasapplied onto an aluminum (Al) collector, followed by drying, to providea cathode.

Next, 95 wt % of artificial graphite as an anode active material and 5wt % of PVDF as a binder were added to NMP to form anode slurry, which,in turn, was applied to a copper (Cu) collector, followed by drying, toprovide an anode.

Then, 1M LiPF₆ was dissolved into a non-aqueous electrolyte containingethylene carbonate (EC) and ethyl methyl carbonate (EMC) in a ratio of1:2 (v:v, EC:EMC) to provide an electrolyte.

A porous polyethylene film was used as a separator, and the structurefor an electrochemical device obtained according to Example 1 was usedas a center pin.

The strip-like anode and the strip-like cathode were stacked on theseparator, and wound around the center pin many times to provide a jellyroll-like structure. The jelly roll-like structure was received in abattery can having an outer diameter of 18 mm and a height of 65 mm, andinsulation plates were disposed on the top and bottom surfaces of theelectrodes. Additionally, an anode lead formed of nickel was drawn fromthe anode collector and welded to the battery can. A cathode lead formedof aluminum was drawn from the cathode collector and welded to analuminum pressure regulating valve mounted on the battery cover.Finally, the electrolyte was injected thereto to provide a battery.

Example 4 Manufacture of Electrochemical Device

A battery was provided in the same manner as described in Example 3,except that the structure for an electrochemical device according toExample 2 was used instead of the structure for an electrochemicaldevice according to Example 1.

Comparative Example 1 Manufacture of Electrochemical Device

A battery was provided in the same manner as described in Example 3,except that a conventional stainless hollow cylindrical tube (Dong JinIndustries, Co. 3Φ center pin made of iron) not sealed at both endsthereof was used instead of the structure for an electrochemical deviceaccording to Example 1.

Experimental Example 1 Evaluation of Overcharge Safety of Battery

The following experiment was performed by using the batteries accordingto Example 3 and Comparative Example 1 to evaluate the safety thereof.Each battery having a capacity of 2400 mAh was fully charged to 4.2V at0.5C, and then the overcharge test was performed. The overcharge testwas performed to 13.5V at 2C. During the test, the surface of eachbattery was insulated perfectly from heat to simulate a conditionsimilar to the condition in a battery pack. Herein, the time requiredfor the CID to cause a short, and the temperature and voltage of thebattery were measured. The results are shown in FIGS. 8 and 9.

As shown in FIGS. 8 and 9, the battery according to Example 3 shows areduced time required for the CID to cause a short as compared to thebattery according to Comparative Example 1 (20 minutes vs. 17 minutes),and a reduced peak temperature. This demonstrates that theelectrochemical device (Example 3) using the structure according to thepresent invention has improved safety.

Experimental Example 2 High-Temperature Storage Test

The following thermal impact test was performed to evaluate thehigh-temperature safety of the batteries according to Example 3 andComparative Example 1. Each battery was fully charged to 4.2V at 0.5C,heated to 75° C., maintained at the same temperature for 6 hours, cooledto −40° C., and maintained at the same temperature for 6 hours. Theabove cycle was repeated 12 times, and the drop in the voltage of eachbattery and the increment in the resistance of each battery wereobserved. The results are shown in the following Table 1.

TABLE 1 Before storage After storage Vol (V) Imp (Ω) Vol (V) Imp (Ω) Ex.3 4.1763 54.45 4.1325 57.48 Comp. Ex. 1 4.1758 55.61 4.1359 58.71

As shown in Table 1, the batteries according to Example 3 andComparative Example 1 show similar results of drop in the voltage andthe increment in the resistance after repeating the heating/coolingcycles. Therefore, it can be seen from the above results that thepresence of the structure for an electrochemical device according to thepresent invention does not adversely affect the quality of the battery.

INDUSTRIAL APPLICABILITY

As can be seen from the foregoing, the structure for an electrochemicaldevice according to the present invention is a sealed structure having ahollow space therein, comprises a material capable of improving thesafety of the electrochemical device using the same by generating gasesvia thermal decomposition in the hollow space, and allows easy controlof the amount of the material contained in the hollow space.

Additionally, the structure according to the present invention does notaffect an electrochemical device when the device is in a normaltemperature/voltage condition. However, when the internal temperature ofthe device abnormally increases or the device is subjected to anover-voltage state due to overcharge, a predetermined portion of thestructure may melt. Such melting of a portion of the structure causesthe inner part of the structure to be exposed to the exterior. At thistime, the material contained in the hollow space of the structure, i.e.the material capable of generating gases via thermal decomposition isdischarged to the exterior of the structure, before or after it isthermally decomposed to generate gases. The gases (carbon dioxide and/ornitrogen) generated at the exterior of the structure or discharged tothe exterior of the structure can contribute to improvement of thesafety of the device.

Further, the gases allow early operation of the safety device providedin the device, thereby improving the safety of the device.

Although several preferred embodiments of the present invention havebeen described for illustrative purposes, those skilled in the art willappreciate that various modifications, additions and substitutions arepossible, without departing from the scope and spirit of the inventionas disclosed in the accompanying claims.

The invention claimed is:
 1. A structure suitable for use in anelectrochemical device comprising: a tube having two or more hollowcylindrical tubes formed of a polymer or a metal connected to each otherlongitudinally by way of a polymer; a third member formed of a polymeror a metal for sealing one end of the tube; and a fourth member formedof a polymer or a metal for sealing the other end of the tube, thestructure further comprising a material generating inert gases viathermal decomposition in a hollow space thereof, wherein the polymer orthe metal of the two or more hollow cylindrical tubes has a highermelting point than the melting point of the polymer or the metal of thethird member and the polymer or the metal of the fourth member.
 2. Thestructure as claimed in claim 1, wherein the polymer connecting the twoor more hollow cylindrical tubes melts at a temperature higher than anormal drive temperature of the device or at a voltage higher than 4.3V.3. The structure as claimed in claim 1, wherein the material generatinginert gases via thermal decomposition is at least one compound selectedfrom the group consisting of organic peroxides, carbonate compounds, azocompounds, hydrazide compounds and carbazide compounds.
 4. The structureas claimed in claim 1, wherein the polymer connecting the two or morehollow cylindrical tubes is at least one polymer selected from the groupconsisting of silicone resins, acrylic resins, urethane resins, epoxyresins, rubber, polyethylene, polypropylene, polybutene,polyacetaldehyde, polyformaldehyde, polypropylene oxide, polymethylmethacrylate, polyvinylidene chloride, polyvinyl fluoride andpolyvinylidene fluoride.
 5. The structure as claimed in claim 1, whereineach of the hollow cylindrical tube, the third member and the fourthmember is independently formed of a polymer or a metal.
 6. Anelectrochemical device comprising a cathode, an anode, a separator, anelectrolyte, a casing for the device, and a structure for anelectrochemical device comprising a tube having two or more hollowcylindrical tubes formed of a polymer or a metal connected to each otherlongitudinally by way of a polymer; a third member formed of a polymeror a metal for sealing one end of the tube; and a fourth member formedof a polymer or a metal for sealing the other end of the tube, thestructure further comprising a material generating inert gases viathermal decomposition in a hollow space thereof, wherein the polymer orthe metal of the two or more hollow cylindrical tubes has a highermelting point than the melting point of the polymer or the metal of thethird member and the polymer or the metal of the fourth member.
 7. Theelectrochemical device as claimed in claim 6, which is a secondarybattery.
 8. The electrochemical device as claimed in claim 6, whereinthe structure is received in a hollow space in the device, contained inthe electrolyte, or included as a center pin.
 9. The electrochemicaldevice as claimed in claim 6, wherein the material contained in thehollow space in the structure generates inert gases via thermaldecomposition before or after it is discharged to the exterior of thestructure, at a temperature higher than a normal drive temperature ofthe device or at a voltage higher than 4.3V.
 10. The electrochemicaldevice as claimed in claim 6, which further comprises: (a) a firstsafety device that detects variations in the pressure inside theelectrochemical device to interrupt charging of the electrochemicaldevice or to convert a charging condition into a discharging condition;(b) a second safety device that detects variations in the pressureinside the electrochemical device to emit the heat or gas present insidethe electrochemical device; or (c) both the first safety device and thesecond safety device, wherein the material contained in the hollow spaceof the structure generates inert gases via thermal decomposition beforeor after it is discharged to the exterior of the structure, at atemperature higher than a normal drive temperature of the device or at avoltage higher than 4.3V, and either or both of the first safety deviceand the second safety device operate by detecting variations in theinternal pressure of the device increased by the gases generated in theexterior of the structure or discharged to the exterior of thestructure.